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Single-cell image associated with Big t cellular immunotherapy reactions throughout vivo.
The controlled growth of surface-supported metal nanoparticles (NPs) is essential to a broad range of applications. To this end, we explore the seeded growth of highly ordered arrays of substrate-supported Au NPs through a fully orthogonal design of experiment (DoE) scheme applied to a reaction system consisting of HAuCl4, citrate, and hydrogen peroxide. Scanning electron microscopy in combination with digital image analysis (DIA) is used to quantitatively characterize the resultant NP populations in terms of both particle and array features. The effective optical properties of the NP arrays are additionally analyzed using spectroscopic ellipsometry (SE), allowing characteristics of the localized surface plasmon resonances (LSPRs) of the arrays to be quantified. We study the dependence of the DIA- and SE-extracted features on the different reagent concentrations through modeling using multiple linear regression with backward elimination of independent variables. A process window is identified for which uniform arrays of quasi-spherical Au NPs are grown over large surface areas. Aside from reagent concentrations the system is highly sensitive to the hydrodynamic conditions during the deposition. This issue is likely caused by an Au precursor mass-transport limitation of the reduction reaction and it is found that agitation of the growth medium is best avoided to ensure a macroscopically even deposition. Parasitic homogeneous nucleation can also be a challenge and was separately studied in a full DoE scheme with equivalent growth media but without substrates, using optical tracking of the solutions over time. Conditions yielding quasi-spherical surface-supported NPs are found to also be affiliated with strong tendencies for parasitic homogeneous nucleation and thereby loss of Au precursor, but addition of polyvinyl alcohol can possibly help alleviate this issue.Phosphoinositides are minor components of cell membranes, but play crucial roles in numerous signal transduction pathways. To obtain quantitative measures of phosphoinositides, sensitive, accurate, and comprehensive methods are needed. Here, we present a quantitative targeted ion chromatography-mass spectrometry-based workflow that separates phosphoinositide isomers and increases the quantitative accuracy of measured phosphoinositides. Besides testing different analytical characteristics such as extraction and separation efficiency, the reproducibility of the developed workflow was also investigated. The workflow was verified in resting and stimulated human platelets, fat cells, and rat hippocampal brain tissue, where the LOD and LOQ for phosphoinositides were at 312.5 and 625 fmol, respectively. The robustness of the workflow is shown with different applications that confirms its suitability to analyze multiple less-abundant phosphoinositides.We introduce a method called restrain-free energy perturbation-release 2.0 (R-FEP-R 2.0) to estimate conformational free energy changes of protein loops via an alchemical path. R-FEP-R 2.0 is a generalization of the method called restrain-free energy perturbation-release (R-FEP-R) that can only estimate conformational free energy changes of protein side chains but not loops. The reorganization of protein loops is a central feature of many biological processes. Unlike other advanced sampling algorithms such as umbrella sampling and metadynamics, R-FEP-R and R-FEP-R 2.0 do not require predetermined collective coordinates and transition pathways that connect the two endpoint conformational states. The R-FEP-R 2.0 method was applied to estimate the conformational free energy change of a β-turn flip in the protein ubiquitin. The result obtained by R-FEP-R 2.0 agrees with the benchmarks very well. We also comment on problems commonly encountered when applying umbrella sampling to calculate protein conformational free energy changes.The emerging demand for device miniaturization and integration prompts the patterning technique of micronano-cross-scale structures as an urgent desire. Lithography, as a sufficient patterning technique, has been playing an important role in achieving functional micronanoscale structures for decades. As a promising alternative, we have proposed and demonstrated the maskless optical projection nanolithography (MLOP-NL) technique for efficient cross-scale patterning. A minimum feature size of 32 nm, which is λ/12 super resolution breaking the optical diffraction limit, has been achieved by a single exposure. Furthermore, multiscale two-dimensional micronano-hybrid structures with the size over hundreds of micrometers and the precision at tens of nanometers have been fabricated by simply controlling the exposure conditions. The proposed MLOP-NL technique provides a powerful tool for achieving cross-scale patterning with both large-scale and precise configuration with high efficiency, which can be potentially used in the fabrication of multiscale integrated microsystems.Auger recombination is the main nonradiative process in multicarrier states of high-quality quantum dots (QDs). For the most-studied CdSe/CdS core/shell QDs, we effectively reduce the biexciton Auger rate by enhancing dielectric screening of band-edge carriers via epitaxial growth of additional ZnS shells. Super volume scaling of negative-trion Auger lifetime for CdSe/CdS core/shell QDs is achieved with the outermost ZnS shells. The volume of CdSe/CdS/ZnS QDs can be less than half that of CdSe/CdS QDs with the same negative-trion Auger lifetime. Auger suppression by the ZnS shells is more pronounced for QDs with wave functions of band-edge carriers spreading close to the inorganic-organic interface, such as CdSe/CdS QDs with small cores. A maximum drop of biexciton Auger rate of ∼50% and a maximum enhancement of biexciton emission quantum yield of 75% are achieved. Fluorofurimazine Auger engineering by dielectric screening opens up new opportunities to improve the emission properties of multicarrier states in QDs.We report the efficient synthesis of cycloalkyl-fused naphthalenes through the [4 + 2]-cycloaddtion/decarboxylative aromatization of alkyne-tethered aryne insertion adducts. These scaffolds were difficult to synthesize using conventional reactions. The reaction proceeds via the formation of a benzopyrylium intermediate followed by intramolecular [4 + 2] cycloaddition and a subsequent decarboxylation pathway. This method is also compatible with allene-tethered substrates to afford similar products. In addition, the one-pot synthesis of polysubstituted naphthalenes via aryne insertion/benzannulation has also been developed in good yield.
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